Liquid composition for imparting alcohol-repellency to semiconductor substrate material, and method for treating surface of semiconductor substrate using said liquid composition

ABSTRACT

A liquid composition for imparting alcohol-repellency to a semiconductor substrate material and a method for treating a semiconductor substrate surface using the liquid composition, are disclosed. The liquid composition contains: a surfactant (A) having a substituent of formula (1) (where n is an integer of 3 to 20), and an anionic hydrophilic group; and a compound (B) being selected from the group consisting of compounds having a polyethylenimine and a substituent of formula (2) or formula (3) (where R 1 , R 2 , R 3  and R 4  are each independently hydrogen or a C1-6 alkyl, alkenyl, alkynyl, or aryl, and X −  is a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a fluoroborate ion, a phosphate ion, an acetate ion, a trifluoroacetate ion, a sulfate ion, a hydrogen sulfate ion, a methane sulfate ion, a hydroxide ion, a perchlorate ion, or a nitrate ion).

TECHNICAL FIELD

The present invention relates to a liquid composition for impartingalcohol-repellency to a semiconductor substrate material, and a methodfor treating a surface of a semiconductor substrate by using the same.

BACKGROUND ART

A process of fabricating a semiconductor device includes a step offorming fine unevenness on a surface of a semiconductor substrate. Suchfine unevenness is generally formed by a method like the followingmethod. Specifically, a photoresist is uniformly applied onto a surfaceof a flatly deposited semiconductor substrate material to provide aphotosensitive layer, which is then subjected to selective exposure anddevelopment to provide a desired photoresist pattern. Subsequently,using this photoresist pattern as a mask, a semiconductor substratematerial to be provided with unevenness is subjected to dry etching toform a desired pattern on said thin film. Then, the photoresist patternand the residue resulting from the dry etching are completely removedwith a removal solution and a cleaning solution. Thereafter, the surfaceis rinsed with pure water remove said removal solution and cleaningsolution therefrom. This pure water is removed and dried from thesemiconductor substrate by rotating the substrate at a high speed.

Due to the micronization of the design rule, rise of the height andreduction of the line width of the finely uneven pattern have increasedthe aspect ratio thereof. When such a high aspect ratio pattern isrinsed with water, the pattern may collapse due to the capillary forceof water. The capillary force is proportional to the surface tension.Accordingly, in order to solve this problem, isopropyl alcohol(hereinafter, referred to as “IPA”) whose surface tension is smallerthan water is used for rinsing. However, if the aspect ratio (patternheight/line width) is, for example, as high as 25 where the finelyuneven pattern has a height of 500 nm and a line width of 20 nm, thepattern collapse may occur even when IPA is used for rinsing. Therefore,such an IPA treatment alone is insufficient.

The method for solving the problem of such pattern collapse may be amethod in which the pattern surface is hydrophobized to make the contactangle between the pattern and water closer to 90 degrees, therebypreventing pattern collapse upon rinsing with water.

The pattern, however, has minute unevenness and such surface unevennessaffects the contact angle. Therefore, even if the contact angle withpure water is 90 degrees on a flat plane, it is impossible to completelyeliminate the force associated with collapse in the actual pattern.Furthermore, a force resulting from surface tension is also applied tothe pattern. Since this force is expressed as the product of the sine ofthe contact angle and the surface tension, it becomes large when thecontact angle is 90 degrees. Therefore, in a recent unconventionallyhigh aspect ratio pattern, collapse of the pattern is becoming lesslikely to be prevented only by hydrophobizing the pattern surface asdescribed above.

In order to solve this problem, alcohols that have lower surface tensionthan water, for example, IPA can be used for cleaning, but even when IPAis used, an IPA repelling technology is strongly required for making thecontact angle between IPA and the pattern larger to prevent thecollapse.

In Patent Literatures 1, 2 and 3, a method for treating a surface of asemiconductor substrate is proposed, which includes: subjecting thesemiconductor substrate to wetting treatment using a liquid chemical;removing the liquid chemical with pure water, forming a water-repellentprotective film on the surface of the semiconductor substrate; rinsingthe semiconductor substrate with pure water; and drying thesemiconductor substrate. Moreover, a silane-based compound is proposedas an agent for forming the water-repellent protective film.

Patent Literature 4 proposes a surface treating agent that can be usedfor treating surfaces of various base materials, including asilane-based compound having a fluorocarbon group, an acid catalyst anda liquid or solid medium.

Patent Literature 5 proposes a surface treating agent containing acopolymer of acrylic ester having a linear C6 perfluoroalkyl group andmethacrylic ester having a linear C6 perfluoroalkyl group, as a surfacetreating agent having IPA-repellency that is applicable to treatments ofsurfaces of various base materials.

CITATION LIST Patent Literatures

Patent Literature 1: Japanese Unexamined Patent Application PublicationNo. 2010-114414

Patent Literature 2: Japanese Unexamined Patent Application PublicationNo. 2014-197638

Patent Literature 3: Japanese Unexamined Patent Application PublicationNo. 2014-197571

Patent Literature 4: Japanese Unexamined Patent Application PublicationNo. Heisei 9-31449

Patent Literature 5: International Publication No. WO2010/113646

SUMMARY OF INVENTION Technical Problem

The inventions of Patent Literatures 1-5, however, have technicalproblems as described below.

Patent Literature 1 describes a method for treating a surface of asemiconductor substrate, comprising hexamethyldisilazane ortrimethylsilyl dimethylamine. Patent Literature 2 discloses use ofoctyldimethylsilyl dimethylamine or trimethylsilyl dimethylamine, andPatent Literatures 3 and 4 each propose a method for forming awater-repellent protective film with tetramethylsilane and asilane-based compound such as perfluorodecyl trimethoxysilane,respectively. With the water-repellent protective films disclosed inthese literatures, however, the contact angle between the materialformed on the semiconductor substrate and the alcohol is insufficientand thus cannot be employed for the purpose of the present invention(for example, Comparative examples 23-50).

A surface treating agent containing the copolymer described in PatentLiterature 5 can be applied and dried on a surface of a semiconductorsubstrate to impart oil-repellency to the surface of the semiconductorsubstrate. When, however, IPA is used for rinsing without drying thesurface treating agent, the surface treating agent on the semiconductorsubstrate flows out without curing and therefore an oil-repellent filmcannot be formed (for example, Comparative examples 51-54).

On the other hand, when said surface treating agent is dried, a thickfilm is formed on the semiconductor substrate, which may interfere thesubstrate to exert proper functions as a semiconductor.

Under such circumstances, there have been needs to provide a liquidcomposition for imparting alcohol-repellency to a surface of a materialconstituting a semiconductor substrate, and a method for treating asurface of a semiconductor substrate using the same.

Solution to Problem

The present invention provides a method for solving the above-describedproblems. The present invention comprises a liquid composition and amethod for treating a surface of a semiconductor substrate shown below.

1. A liquid composition for imparting alcohol-repellency to asemiconductor substrate material, comprising 0.01-15% by mass of asurfactant (A) shown below, and 0.0001-20% by mass of a compound (B)shown below having a weight-average molecular weight of 200-500000 and4-30 mmol of an amino group per gram.

Surfactant (A): a surfactant having a substituent represented by Generalformula (1) below and an anionic hydrophilic group

Compound (B): Polyethylenimine or a compound having a substituentrepresented by General formula (2) or (3) below:

[Chemical formula 1]

C_(n)F_(2n+1)—  (1)

where n is an integer of 3-20,

where R¹ and R² are hydrogen or a C1-6 alkyl, alkenyl, alkynyl or arylgroup,

where R³ and R⁴ are hydrogen or a C1-6 alkyl, alkenyl, alkynyl or arylgroup, and

X⁻ represents a fluoride ion, a chloride ion, a bromide ion, an iodideion, a fluoroborate ion, a phosphate ion, an acetate ion, atrifluoroacetate ion, a sulfate ion, a hydrogen sulfate ion, a methanesulfate ion, a hydroxide ion, a perchlorate ion or a nitrate ion.

2. The liquid composition according to Item 1, wherein the anionichydrophilic group has a structure represented by Formula (4), (5), (6)or (7) below:

where R⁵ and R⁶ represent hydrogen or a C1-6 alkyl, alkenyl, alkynyl oraryl group,

where R⁷ and R⁸ represent hydrogen or a C1-6 alkyl, alkenyl, alkynyl oraryl group,

where Z represents a metal, hydrogen or a quaternary amine,

where Z represents a metal, hydrogen or a quaternary amine.

3. The liquid composition according to Item 1, wherein the compound (B)having a weight-average molecular weight of 200-500000 and having 4-30mmol of an amino group per gram is a homopolymer or a copolymercomprising one or more compounds selected from the following as astarting material monomer: ethyleneimine, prop-2-en-1-amine,N-methylprop-2-en-1-amine, N,N-dimethylprop-2-en-1-amine,N-ethylprop-2-en-1-amine, N-ethyl-N-methylprop-2-en-1-amine,N,N-diethylprop-2-en-1-amine, 2-methylprop-2-en-1-amine,N,2-dimethylprop-2-en-1-amine, N,N,2-trimethylprop-2-en-1-amine,N-ethyl-2-methylprop-2-en-1-amine,N-ethyl-N,2-dimethylprop-2-en-1-amine,N,N-diethyl-2-methylprop-2-en-1-amine, but-2-en-1-amine,N-methylbut-2-en-1-amine, N,N-dimethylbut-2-en-1-amine,N-ethylbut-2-en-1-amine, N-ethyl-N-methylbut-2-en-1-amine,N,N-diethylbut-2-en-1-amine, 2-methylbut-2-en-1-amine,N,2-dimethylbut-2-en-1-amine, N,N,2-trimethylbut-2-en-1-amine,N-ethyl-2-methylbut-2-en-1-amine, N-ethyl-N,2-dimethylbut-2-en-1-amine,N,N-diethyl-2-methylbut-2-en-1-amine, 2,3-dimethylbut-2-en-1-amine,N,2,3-trimethylbut-2-en-1-amine, N,N,2,3-tetramethylbut-2-en-1-amine,N-ethyl-2,3-dimethylbut-2-en-1-amine,N-ethyl-N,2,3-trimethylbut-2-en-1-amine,N,N-diethyl-2,3-dimethylbut-2-en-1-amine, diallylamine,N-allyl-N-methylprop-2-en-1-amine, N-allyl-N-ethylprop-2-en-1-amine,N-allyl-N,N-dimethylprop-2-en-1-amine, and a hydrochloride, a sulfate, aphosphate, a nitrate and a sulfur dioxide thereof.4. The liquid composition according to Item 1, wherein the surfactant(A) isN,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diaminedioxide,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluoropentylpropyl)propan-1,3-diaminedioxide,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorobutylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluoropentylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluorobutylpropyl)propane-1,3-diaminedioxide,perfluorohexadecanoic acid, perfluoropentadecanoic acid,perfluorotetradecanoic acid, perfluorotridecanoic acid,perfluorododecanoic acid, perfluoroundecanoic acid, perfluorodecanoicacid, perfluorononanoic acid, perfluorooctanoic acid, perfluoroheptanoicacid, perfluorohexanoic acid, perfluoropentanoic acid, perfluorobutanoicacid, perfluorooctanesulfonic acid, perfluoroheptanesulfonic acid,perfluorohexanesulfonic acid, perfluoropentanesulfonic acid,perfluorobutanesulfonic acid, perfluoropropanesulfonic acid,perfluorooctylphosphonic acid, perfluoroheptylphosphonic acid,perfluorohexylphosphonic acid, perfluoropentylphosphonic acid,perfluorobutylphosphonic acid, perfluoropropylphosphonic acid,(1H,1H,2H,2H-perfluorodecyl)phosphonic acid,(1H,1H,2H,2H-perfluorononyl)phosphonic acid,(1H,1H,2H,2H-perfluorooctyl)phosphonic acid,(1H,1H,2H,2H-perfluoroheptyl)phosphonic acid,(1H,1H,2H,2H-perfluorohexyl)phosphonic acid,(1H,1H,2H,2H-perfluoropentyl)phosphonic acid, a compound represented byany one of Formulae (8)-(11) below:

[Chemical formula 8]

[CF₃(CF₂)_(m)(CH₂)₂OCH₂CH(OH)CH₂O]₂(O)POH  (8)

-   -   where m is an integer of 2-7,

[Chemical formula 9]

[CF₃(CF₂)_(k)CH(OH)CH₂O]₂(O)POH  (9)

-   -   where k is an integer of 2-7,

[Chemical formula 10]

[CF₃(CF₂)_(j)(CH₂)₂OCH₂CH(OH)CH₂O](O)P(OH)₂  (10)

-   -   where j is an integer of 2-7,

[Chemical formula 11]

[CF₃(CF₂)_(h)CH(OH)CH₂O](O)P(OH)₂  (11)

-   -   where h is an integer of 2-7,        and a metal salt or an ammonium salt thereof.        5. The liquid composition for a semiconductor substrate        according to Item 1, wherein the alcohol showing        alcohol-repellency is isopropyl alcohol.        6. The liquid composition according to Item 1, wherein the        semiconductor substrate material is one or more selected from        silicon, aluminium, an aluminium-copper alloy, tantalum, nickel,        tungsten, cobalt, molybdenum, titanium, zirconium, ruthenium,        hafnium, platinum, silicon-germanium, germanium, and an oxide, a        nitride and a carbide thereof.        7. A method for treating a surface of a semiconductor substrate        by bringing a liquid composition into contact with the        semiconductor substrate to form an alcohol-repellent film on the        semiconductor substrate, the method comprising the steps of:        bringing the surface of the semiconductor material into contact        with a liquid composition containing 0.01-15% by mass of a        surfactant (A) shown below and 0.0001-20% by mass of a        compound (B) shown below having a weight-average molecular        weight of 200-500000 and having 4-30 mmol of an amino group per        gram.

Surfactant (A): a surfactant having a substituent represented by Generalformula (1) below and an anionic hydrophilic group.

Compound (B): Polyethylenimine or a compound having a substituentrepresented by General formula (2) or (3) below.

8. The method for treating a surface of a semiconductor substrateaccording to Item 7, wherein the alcohol-repellency is isopropylalcohol-repellency.9. The method for treating a surface of a semiconductor substrateaccording to Item 7, wherein the semiconductor substrate is one or moreselected from silicon, aluminium, an aluminium-copper alloy, tantalum,nickel, tungsten, cobalt, molybdenum, titanium, zirconium, ruthenium,hafnium, platinum, silicon-germanium, germanium, and an oxide, a nitrideand a carbide thereof.

Advantageous Effects of Invention

In a preferable aspect of the present invention, a liquid compositionand a method for treating a surface of a semiconductor substrate of thepresent invention can be used to prevent collapse of various materialpatterns having a high aspect ratio formed on a semiconductor substrateduring a process of fabricating a semiconductor device, and thus beingcapable of manufacturing a high precision and high quality semiconductordevice at high yield.

DESCRIPTION OF EMBODIMENTS

The liquid composition of the present invention is a liquid compositioncontaining a surfactant (A) having a substituent represented by Formula(1) and an anionic hydrophilic group, and a compound (B) selected fromthe group consisting of a compound having a substituent represented byFormula (2) or (3) and polyethylenimine.

Specifically, a liquid composition of the present invention is a liquidcomposition for imparting alcohol-repellency to a semiconductorsubstrate material, comprising:

0.01-15% by mass of a surfactant (A) having a substituent represented byFormula (1):

[Chemical formula 12]

C_(n)F_(2n+1)—  (1)

where, n is an integer of 3-20, and an anionic hydrophilic group; and

0.0001-20% by mass of a compound (B) having a weight-average molecularweight of 200-500000 and having 4-30 mmol of an amino group per gram,selected from the group consisting of polyethylenimine and a compoundhaving a substituent represented by Formula (2) or (3):

where, R¹ and R² each independently represent hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group,

where, R³ and R⁴ each independently represent hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group, and X⁻ represents a fluoride ion, achloride ion, a bromide ion, an iodide ion, a fluoroborate ion, aphosphate ion, an acetate ion, a trifluoroacetate ion, a sulfate ion, ahydrogen sulfate ion, a methane sulfate ion, a hydroxide ion, aperchlorate ion or a nitrate ion.

Although the mechanism of how the liquid composition of the presentinvention imparts alcohol-repellency to a surface of a semiconductorsubstrate is not clear, a surfactant (A) having a substituentrepresented by Formula (1) and an anionic hydrophilic group, and acompound (B) selected from the group consisting of a compound having asubstituent represented by Formula (2) or (3) and polyethylenimine,which are used in the liquid composition of the present invention, areconsidered to adsorb and manifest alcohol-repellency on the surface ofthe semiconductor substrate material. The alcohol-repellency in thiscase is evaluated to be acceptable when the contact angle betweenalcohol and a material surface treated by making contact with the liquidcomposition of the present invention is 30° or more.

The anionic hydrophilic group of the surfactant (A) used with thepresent invention has a structure represented by Formula (4), (5), (6)or (7):

where, R⁵ and R⁶ each independently represent hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group,

where, R⁷ and R⁸ each independently represent hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group,

where, Z represents a metal, hydrogen or a quaternary amine,

where, Z represents a metal, hydrogen or a quaternary amine.

In a preferable aspect of the present invention, R⁵, R⁶, R⁷ and R⁸ inthe formulae shown above each independently represent hydrogen or a C1-6alkyl group, preferably a methyl group, an ethyl group or a propylgroup, and more preferably hydrogen.

Moreover, Z is preferably hydrogen or a quaternary amine and morepreferably hydrogen.

In the surfactant (A) having a substituent represented by Formula (1)and an anionic hydrophilic group used with the present invention, theminimum value of the carbon number n of the substituent represented byFormula (1) is 3 or higher, preferably 4 or higher and particularlypreferably 6 or higher, while the maximum value is 20 or lower,preferably 12 or lower and particularly preferably 8 or lower.

The concentration range of the surfactant (A) having a substituentrepresented by Formula (1) and an anionic hydrophilic group in theliquid composition of the present invention is 0.01-20% by mass,preferably 0.05% by mass and more preferably 0.1% by mass or more, andpreferably 15% by mass or less and more preferably 5% by mass or less.In particular, the concentration range of the surfactant (A) in theliquid composition of the present invention is preferably 0.05-15% bymass and more preferably 0.1-5% by mass.

Furthermore, if solubility of these compounds in water is insufficientand phase separation occurs, an organic solvent such as an alcohol maybe added. Also, a commonly used acid or alkali may be added tocomplement solubility. Even if no phase separation but simply cloudingoccurs, they may be used within a range that does not impair the effectof the treatment liquid or they may be used with stirring to give ahomogenous treatment liquid. Moreover, in order to avoid clouding of thetreatment liquid, an organic solvent such as an alcohol, acid or alkalimay be added before use as described above.

Examples of the surfactant (A) having a substituent represented byFormula (1) and an anionic hydrophilic group used with the presentinvention include, but not limited to,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diaminedioxide,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluoropentylpropyl)propane-1,3-diaminedioxide,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorobutylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluoropentylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluorobutylpropyl)propane-1,3-diaminedioxide,perfluorohexadecanoic acid, perfluoropentadecanoic acid,perfluorotetradecanoic acid, perfluorotridecanoic acid,perfluorododecanoic acid, perfluoroundecanoic acid, perfluorodecanoicacid, perfluorononanoic acid, perfluorooctanoic acid, perfluoroheptanoicacid, perfluorobexanoic acid, perfluoropentanoic acid, perfluorobutanoicacid, perfluorooctanesulfonic acid, perfluoroheptanesulfonic acid,perfluorohexanesulfonic acid, perfluoropentanesulfonic acid,perfluorobutanesulfonic acid, perfluoropropanesulfonic acid,perfluorooctylphosphonic acid, perfluoroheptylphosphonic acid,perfluorohexylphosphonic acid, perfluoropentylphosphonic acid,perfluorobutylphosphonic acid, perfluoropropylphosphonic acid,(1H,1H,2H,2H-perfluorodecyl)phosphonic acid,(1H,1H,2H,2H-perfluorononyl)phosphonic acid,(1H,1H,2H,2H-perfluorooctyl)phosphonic acid,(1H,1H,2H,2H-perfluoroheptyl)phosphonic acid,(1H,1H,2H,2H-perfluorohexyl)phosphonic acid,(1H,1H,2H,2H-perfluoropentyl)phosphonic acid, compounds represented byFormulae (8)-(11):

[Chemical formula 19]

[CF₃(CF₂)_(m)(CH₂)₂OCH₂CH(OH)CH₂O]₂(O)POH  (8)

-   -   where m is an integer of 2-7,

[Chemical formula 20]

[CF₃(CF₂)_(k)CH(OH)CH₂]₂(O)POH  (9)

-   -   where k is an integer of 2-7,

[Chemical formula 21]

[CF₃(CF₂)_(j)(CH₂)₂OCH₂CH(OH)CH₂O](O)P(OH)₂  (10)

-   -   where j is an integer of 2-7,

[Chemical formula 22]

[CF₃(CF₂)_(h)CH(OH)CH₂O](O)P(OH)₂  (11)

-   -   where h is an integer of 2-7,        and metal salts and ammonium salts thereof.        Compounds other than these may be used as long as the objective        of the present invention can be achieved.

One type of surfactant (A) may be used alone, or two or more types ofsurfactants (A) may be used in combination.

The compound (B) selected from the group consisting of a compound havinga substituent represented by Formula (2) or (3) and polyethylenimineused with the present invention has 4-30 mmol of an amino group per gramof the compound. The term “amino group” used herein refers to an aminogroup represented by Formula (2) or (3). The minimum value of the aminogroup in the compound (B) is preferably 5 mmol or more and particularlypreferably 6 mmol or more per gram of the compound, while the maximumvalue is preferably 28 mmol or less and particularly preferably 25 mmolor less per gram of the compound, although the maximum value is notparticularly required.

The minimum value of the weight-average molecular weight of the compoundhaving a substituent represented by Formula (2) or (3) orpolyethylenimine used with the present invention is 200 or more andpreferably 300 or more, while the maximum value is 500000 or less andpreferably 200000 or less, although the maximum value is notparticularly required. Herein, the term “weight-average molecularweight” refers to a weight-average molecular weight in terms ofpolystyrene standard as determined by gel permeation chromatography(GPC).

The concentration range of the compound (B) selected from the groupconsisting of the compound having a substituent represented by Formula(2) or (3) and polyethylenimine used with the present invention is0.0001-20% by mass, preferably 0.001% by mass or more, more preferably0.01% by mass or more, and preferably 10% by mass or less and morepreferably 5% by mass or less, in total. In particular, theconcentration range of the compound (B) in the liquid composition of thepresent invention is preferably 0.001-10% by mass and more preferably0.01-5% by mass in total.

Furthermore, if solubility of these compounds in water is insufficientand phase separation occurs, an organic solvent such as an alcohol maybe added. Also, a commonly used acid or alkali may be added tocomplement solubility. Even if no phase separation but simply cloudingoccurs, they may be used within a range that does not impair the effectof the treatment liquid or they may be used with stirring to give ahomogenous treatment liquid. Moreover, in order to avoid clouding of thetreatment liquid, an organic solvent such as an alcohol, acid or alkalimay be added before use as described above.

Examples of the compound (B) having a weight-average molecular weight of200-500000, having 4-30 mmol of an amino group per gram, and having asubstituent represented by Formula (2) or (3) include, but not limitedto, homopolymers and copolymers having, as a starting material monomer,one or more compounds selected from prop-2-en-1-amine,N-methylprop-2-en-1-amine, N,N-dimethylprop-2-en-1-amine,N-ethylprop-2-en-1-amine, N-ethyl-N-methylprop-2-en-1-amine,N,N-diethylprop-2-en-1-amine, 2-methylprop-2-en-1-amine,N,2-dimethylprop-2-en-1-amine, N,N,2-trimethylprop-2-en-1-amine,N-ethyl-2-methylprop-2-en-1-amine,N-ethyl-N,2-dimethylprop-2-en-1-amine,N,N-diethyl-2-methylprop-2-en-1-amine, but-2-en-1-amine,N-methylbut-2-en-1-amine, N,N-dimethylbut-2-en-1-amine,N-ethylbut-2-en-1-amine, N-ethyl-N-methylbut-2-en-1-amine,N,N-diethylbut-2-en-1-amine, 2-methylbut-2-en-1-amine,N,2-dimethylbut-2-en-1-amine, N,N,2-trimethylbut-2-en-1-amine,N-ethyl-2-methylbut-2-en-1-amine, N-ethyl-N,2-dimethylbut-2-en-1-amine,N,N-diethyl-2-methylbut-2-en-1-amine, 2,3-dimethylbut-2-en-1-amine,N,2,3-trimethylbut-2-en-1-amine, N,N,2,3-tetramethylbut-2-en-1-amine,N-ethyl-2,3-dimethylbut-2-en-1-amine,N-ethyl-N,2,3-trimethylbut-2-en-1-amine,N,N-diethyl-2,3-dimethylbut-2-en-1-amine, diallylamine,N-allyl-N-methylprop-2-en-1-amine, N-allyl-N-ethylprop-2-en-1-amine,N-allyl-N,N-dimethylprop-2-en-1-amine, and a hydrochloride, a sulfate, aphosphate, a nitrate or a sulfur dioxide thereof. Compounds other thanthese may be used as long as the objective of the present invention canbe achieved.

In particular, the compound (B) is preferably a homopolymer or acopolymer having, as the starting material monomer, one or morecompounds selected from prop-2-en-1-amine,N,N-dimethylprop-2-en-1-amine, diallylamine, and a hydrochloride, asulfate, a phosphate, a nitrate or a sulfur dioxide thereof.

One type of compound (B) may be used alone, or two or more types ofcompounds (B) may be used in combination.

The liquid composition of the present invention can be used to treat andimpart alcohol-repellency to a surface of various materials constitutingsemiconductor substrates. The alcohol against which the liquidcomposition of the present invention can exhibit alcohol-repellency is,but not particularly limited to, preferably methanol, ethanol,1-butanol, 1-propanol, IPA and the like, and particularly preferablyIPA.

Examples of the material of the semiconductor substrate to whichalcohol-repellency is imparted by surface treatment with the liquidcomposition of the present invention preferably include, but not limitedto, those using one or more of silicon, aluminium, an aluminium-copperalloy, tantalum, nickel, tungsten, cobalt, molybdenum, titanium,zirconium, ruthenium, hafnium, platinum, silicon-germanium, germanium oran oxide, a nitride or a carbide thereof.

The liquid composition of the present invention contains a solvent(remnant) in addition to the surfactant (A) and the compound (B).Examples of the solvent include water, an alcohol or a combinationthereof. The alcohol preferably comprises methanol, ethanol, 1-butanol,1-propanol, IPA, ethylene glycol, propylene glycol, glycerin, diethyleneglycol, xylitol, sorbitol, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether, diethylene glycol monobutyl ether anddipropylene glycol monopropyl ether, and particularly preferablycomprises IPA.

If desired, the liquid composition of the present invention may be addedwith an additive conventionally used in a liquid composition for asemiconductor within a range that does not impair the objective of thepresent invention. For example, a defoamer or the like can be added.

The liquid composition of the present invention can be brought intocontact with a semiconductor substrate to impart alcohol-repellency tothe semiconductor substrate.

A method for bringing the liquid composition of the present inventioninto contact with a semiconductor substrate is not particularly limited.For example, a method in which a semiconductor substrate is immersed inthe liquid composition of the present invention, a method in which theliquid composition is allowed to make contact with a semiconductorsubstrate by dropping or spraying, or the like can be employed.

The temperature at which the liquid composition of the present inventionis used is preferably in a range of 20-80° C. and more preferably in arange of 25-70° C., which may appropriately be determined according tothe semiconductor substrate used.

The contact time with the liquid composition of the present invention ispreferably in a range of 0.3-20 minutes and more preferably in a rangeof 0.5-10 minutes, which may appropriately be determined according tothe semiconductor substrate used.

After bringing the liquid composition of the present invention intocontact with a semiconductor substrate, the excessive liquid compositionis preferably removed with an alcohol such as IPA. In addition, thealcohol remaining on the surface is preferably removed, for example, byblowing dry gas. Accordingly, a semiconductor substrate can be impartedwith alcohol-repellency.

EXAMPLES

Hereinafter, the present invention will be described more specificallyby way of examples and comparative examples. The present invention,however, should not be limited in any way to these examples.

<Contact Angle Meter>

Contact angles were measured with Contact Angle Meter Model DM701 fromKyowa Interface Science Co., Ltd. at a temperature of 21-28° C. and ahumidity of 40-60%.

<Experimental Operation>

Hereinafter, the experimental operations of Examples and Comparativeexamples will be described.

A silicon wafer having a film formed from a semiconductor substratematerial was immersed into a liquid composition shown in Table 2, 4, 7,9 or 12 (immersing temperature and immersing time are respectively shownin Tables 3, 5, 8, 10 and 13), and then the excessive liquid compositionwas rinsed off with isopropyl alcohol (IPA). IPA left on the surface wasblown off with dry nitrogen gas. The contact angle between thesurface-treated substrate material and IPA was measured, where an angleof 30 degrees or more was regarded acceptable.

Example 1

The liquid composition (2A) including 1% by mass ofN,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diamineoxide, 1% by mass of PAS-92 (from Nittobo Medical Co., Ltd. adiallylamine hydrochloride-sulfur dioxide copolymer [secondaryamine/SO₂], weight-average molecular weight 5000) and 98% by mass ofwater was used to immerse a silicon nitride substrate at 25° C. for 10minutes, which was then rinsed with IPA and dried. IPA was dropped ontothis substrate to measure the contact angle therebetween. The contactangle was 38 degrees and thus found acceptable (see Table 3).

Examples 2-37

As can be appreciated from Table 3, all of the substrate materials whosesurfaces had been treated with the liquid compositions shown in Table 2in the same manner as Example 1, had contact angles of 30 degrees ormore with IPA, showing that they had alcohol-repellency.

Comparative Example 1

The substrate material whose surface had been treated with the liquidcomposition 4A shown in Table 4 had a contact angle of less than 30degrees with IPA, showing that, even if a compound having a substituentrepresented by Formula (2) or (3) was contained, the treated substratematerial would not exhibit alcohol-repellency if the proportion of theamino group was less than 4 mmol.

Comparative Example 2

The substrate material whose surface had been treated with the liquidcomposition 4B shown in Table 4 had a contact angle of less than 30degrees with IPA, showing that, even if a compound having a substituentrepresented by Formula (2) or (3) was contained, the treated substratematerial would not exhibit alcohol-repellency if the weight-averagemolecular weight was less than 200.

Comparative examples 3 and 4

The substrate materials whose surfaces had been treated with the liquidcompositions 4C and 4D shown in Table 4 had contact angles of less than30 degrees with IPA, showing that 36 the substrate material treated witha liquid composition that did not contain a surfactant having an anionichydrophilic group represented by any one of Formulae (4)-(7) would notexhibit alcohol-repellency.

Comparative Example 5

The substrate material whose surface had been treated with the liquidcomposition 4E shown in Table 4 had a contact angle of less than 30degrees with IPA, showing that the treated substrate material did notexhibit alcohol-repellency if n of the substituent represented byFormula (1) was less than 3.

Comparative Examples 6-11

The substrate materials whose surfaces had been treated with the liquidcompositions 4F-4K shown in Table 4 had contact angles of less than 30degrees with IPA, showing that the treated substrate material would notexhibit alcohol-repellency if the liquid composition did not contain acompound having a substituent represented by Formula (2) or (3) orpolyethylenimine.

Comparative Examples 12-22

The substrate materials whose surfaces had been treated with the liquidcompositions 4L-4V shown in Table 4 had contact angles of less than 30degrees with IPA, showing that the treated substrate material would notexhibit alcohol-repellency if the liquid composition did not contain asurfactant having a substituent represented by Formula (1) and ananionic hydrophilic group.

Comparative Examples 23-42

The effects of the silane-based compounds having an alkyl groupdescribed in Patent Literatures 1, 2 and 3 were compared with the effectof the present invention. Since some of the contact angles between thesubstrate materials whose surfaces had been treated with the liquidcompositions 7A-7D shown in Table 7 and water were large, some surfaceswere found to be modified. The contact angle with IPA, however, was lessthan 30 degrees, and none of the treated substrate materials hadalcohol-repellency.

Comparative Examples 43-50

The effect of the silane-based compound having a fluorine-containingalkyl group described in Patent Literature 4 was compared with theeffect of the present invention. According to the invention described inPatent Literature 4, either or both of a silane-based compound having afluorine-containing alkyl group and an acid catalyst aremicro-encapsulated and mixed, to apply the resultant to a base materialsurface while breaking the microcapsules. By doing so, the silane-basedcompound can be prevented from decomposing during the course fromblending to application. Therefore, the effect of the inventiondescribed in Patent Literature 4 was considered to be reproduciblewithout micro-encapsulation by mixing a silane-based compound and anacid catalyst and immediately using the same for treating a substratematerial. The substrate material whose surface had been treated with theliquid composition 9A shown in Table 9 had a contact angle of less than30 degrees with IPA, and none of the treated substrate materials hadalcohol-repellency.

Comparative Examples 51-54

The effect of a fluorine-based coating agent was compared with theeffect of the present invention. The respective compounds, apolymerization solvent and an initiator were fed into a sealed vessel tothe concentrations shown in Table 11, and allowed to react at 70° C. formore than 18 hours to obtain a polymer 11A. Subsequently, the polymer11A was diluted with a solvent to give the concentration shown in Table12, thereby obtaining the liquid composition 12A. The substrate materialwhose surface had been treated with the liquid composition 12A shown inTable 12 had a contact angle of less than 30 degrees with IPA, and noneof the treated substrates materials had alcohol-repellency.

TABLE 1 Surfactant Type Name/Structure 1AN,N-Diethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diamine oxide 1B [CF₃(CF₂)₅(CH₂)₂OCH₂CH(OH)CH₂O]₂(O)POH 1CPerfluoroheptanoic acid 1D Perfluorobutanesulfonic acid 1E(1H,1H,2H,2H-Perfluorodecyl)phosphonic acid 1F Perfluorododecanoic acid1G Perfluorohexadccanoic acid 1H Perfluoroheptanol 1IPerfluorohexylamine 1J Perfluoropropionic acid

TABLE 2 Surfactant (A) Compound (B) IPA Water Liquid ConcentrationWeight-average Proportion of Concentration Concentration Concentrationcomposition Type % by mass Type molecular weight amino group*1 % by mass% by mass % by mass 2A 1A 1 PAS-92 5000 5 1 0 98 2B 1B 1 PAA-01 1600 181 40 58 2C 1B 1 PAA-08 8000 18 1 40 58 2D 1B 1 PAA-HCL-05 5000 11 1 4058 2E 1B 1 PAA-1112 1000 14 1 40 58 2F 1B 1 PAS-H-1L 8500 7 1 40 58 2G1B 1 Polyethylenimine 300 21 1 40 58 2H 1B 1 Polyethylenimine 300 210.001 40 59 2I 1B 1 Polyethylenimine 300 21 10 40 49 2J 1B 0.05Polyethylenimine 300 21 1 40 59 2K 1B 10 Polyethylenimine 300 21 1 40 492L 1B 1 Polyethylenimine 300 21 1 98 0 2M 1B 1 Polyethylenimine 1800 211 98 0 2N 1B 1 Polyethylenimine 70000 21 1 98 0 2O 1C 1 PAS-92 5000 5 10 98 2P 1C 1 PAS-H-1L 8500 7 1 0 98 2Q 1D 1 PAS-H-10L 200000 7 1 0 98 2R1E 1 PAA-03 3000 18 1 0 98 2S 1F 1 PAA-03 3000 18 1 0 98 2T 1G 1 PAA-033000 18 1 0 98 *1Proportion of amino group: mmol of amino groupcontained per gram of compound PAA-01 from Nittobo Medical Co., Ltd:Allylamine (free) polymer [Homopolymer of primary amine], weight-averagemolecular weight 1600 PAA-03 from Nittobo Medical Co., Ltd: Allylamine(free) polymer [Homopolymer of primary amine], weight-average molecularweight 3000 PAA-08 from Nittobo Medical Co., Ltd: Allylamine (free)polymer [Homopolymer of primary amine], weight-average molecular weight8000 PAA-HCL-05 from Nittobo Medical Co., Ltd: Allylamine hydrochloridepolymer [Homopolymer of primary amine], weight-average molecular weight5000 PAA-1112 from Nittobo Medical Co., Ltd:Allylamine-dimethylallylamine (free) copolymer [Primary/tertiary amine],weight-average molecular weight 1000 PAS-H-1L from Nittobo Medical Co.,Ltd: Diallyldimethyl ammonium chloride polymer [Homopolymer ofquaternary amine], weight-average molecular weight 8500 PAS-H-10L fromNittobo Medical Co., Ltd: Diallyldimethyl ammonium chloride polymer[Homopolymer of quaternary amine], weight-average molecular weight200,000 PAS-92 from Nittobo Medical Co., Ltd: Diallylaminehydrochloride-sulfur dioxide copolymer [Secondary amine/SO₂],weight-average molecular weight 5000 Polyethylenimine from NipponShokubai Co. Ltd: Ethyleneimine polymer, weight-average molecular weight300 Polyethylenimine from Nippon Shokubai Co. Ltd: Ethyleneiminepolymer, weight-average molecular weight 1800 Polyethylenimine fromNippon Shokubai Co. Ltd: Ethyleneimine polymer, weight-average molecularweight 70000

TABLE 3 IPA Liquid contact com- Substrate Temperature/ Immersing angle/Example position material ° C. time/min degree 1 2A Silicon nitride 2510 38 2 2B Silicon nitride 25 2 53 3 2C Silicon nitride 25 2 61 4 2DSilicon nitride 25 2 60 5 2E Silicon nitride 25 2 56 6 2F Siliconnitride 25 2 51 7 2G Silicon nitride 25 2 36 8 2G Silicon nitride 25 1045 9 2G Aluminum 25 2 47 oxide 10 2G Aluminium- 25 2 52 copper alloy 112G Tantalum 25 2 44 12 2G Nickel 25 2 49 13 2G Tantalum 25 2 47 nitride14 2G Tungsten oxide 25 2 54 15 2G Tungsten 25 2 49 16 2G Cobalt 25 2 5117 2G Molybdenum 25 2 55 18 2G Titanium 25 2 39 nitride 19 2G Siliconoxide 25 2 52 20 2G Silicon 25 2 55 21 2H Silicon nitride 25 10 35 22 2ISilicon nitride 25 10 36 23 2J Silicon nitride 25 10 40 24 2K Siliconoxide 25 10 44 25 2L Silicon oxide 25 10 40 26 2M Silicon nitride 25 245 27 2N Silicon nitride 25 2 41 28 2O Silicon nitride 25 10 40 29 2PSilicon nitride 25 10 32 30 2Q Silicon nitride 25 10 33 31 2R Siliconnitride 25 10 52 32 2S Silicon oxide 25 0.25 34 33 2S Silicon oxide 25 146 34 2S Silicon oxide 25 10 54 35 2S Silicon oxide 25 30 43 36 2SSilicon oxide 25 60 52 37 2S Silicon oxide 60 10 48 38 2S Silicon oxide80 10 49 39 2T Silicon nitride 25 10 51

TABLE 4 Surfactant Compound IPA Water Liquid ConcentrationWeight-average Proportion of Concentration Concentration Concentrationcomposition Type % by mass Type molecular weight amino group *1 % bymass % by mass % by mass 4A 1C 1 PAS-2401 2000 3 1 0 98 4B 1C 1N,N′-Bis(3-aminopropyl) 174 23 1 0 98 ethylenediamine 4C 1H 1Polyethylenimine 300 21 1 0 98 4D 1I 1 Polyethylenimine 300 21 1 0 98 4E1J 1 Polyethylenimine 300 21 1 0 98 4F 1A 1 0 99 4G 1B 1 40 59 4H 1C 1 099 4I 1D 1 0 99 4J 1E 1 0 99 4K 1F 1 0 99 4L PAS-92 5000 5 1 0 99 4MPAA-01 1600 18 1 0 99 4N PAA-03 3000 18 1 0 99 4O PAA-08 8000 18 1 0 994P PAA-HCL-05 5000 11 1 0 99 4Q PAA-1112 1000 14 1 0 99 4R PAS-H-1L 85007 1 0 99 4S PAS-H-10L 200000 7 1 0 99 4T Polyethylenimine 300 21 1 0 994U Polyethylenimine 1800 21 1 0 99 4V Polyethylenimine 70000 21 1 0 99PAS-2401 from Nittobo Medical Co., Ltd: Diallylmethyl ethyl ammoniumethyl sulfate-sulfur dioxide copolymer [Quaternary amine/SO₂]

TABLE 5 IPA Com- Liquid contact parative com- Substrate Temperature/Immersing angle/ example position material ° C. time/min degree 1 4ASilicon nitride 25 10 <10 2 4B Silicon nitride 25 10 <10 3 4C Siliconnitride 25 10 <10 4 4D Silicon nitride 25 10 <10 5 4E Silicon nitride 2510 <10 6 4F Silicon nitride 25 10 <10 7 4G Silicon nitride 25 10 28 8 4HSilicon nitride 25 10 <10 9 4I Silicon nitride 25 10 <10 10 4J Siliconnitride 25 10 20 11 4K Silicon nitride 25 10 <10 12 4L Silicon nitride25 10 <10 13 4M Silicon nitride 25 10 <10 14 4N Silicon nitride 25 10<10 15 4O Silicon nitride 25 10 <10 16 4P Silicon nitride 25 10 <10 174Q Silicon nitride 25 10 <10 18 4R Silicon nitride 25 10 <10 19 4SSilicon nitride 25 10 <10 20 4T Silicon nitride 25 10 <10 21 4U Siliconnitride 25 10 <10 22 4V Silicon nitride 25 10 <10

TABLE 6 Silane-based compound Type Name 6A Hexamethyldisilazane 6BOctyldimethylsilyl dimethylamine 6C Trimethylsilyl dimethylamine 6DTetramethylsilane 6E Perfluorodecyl trimethoxysilane

TABLE 7 Liquid Silane-based compound Toluene composition TypeConcentration mass % Concentration mass % 7A 6A 1 99 7B 6B 1 99 7C 6C 199 7D 6D 1 99

TABLE 8 Comparative Liquid Immersing Water contact IPA contact examplecomposition Substrate material Temperature/° C. time/min angle/degreeangle/degree 23 7A Silicon oxide 25 2 19 <10 24 7B Silicon oxide 25 2 89<10 25 7B Silicon nitride 25 2 83 <10 26 7C Silicon oxide 25 2 68 <10 277D Silicon oxide 25 2 <10 <10 28 7A Silicon oxide 60 2 42 <10 29 7BSilicon oxide 60 2 101 <10 30 7B Silicon nitride 60 2 93 <10 31 7CSilicon oxide 60 2 77 <10 32 7D Silicon oxide 60 2 20 <10 33 7A Siliconoxide 25 10 20 <10 34 7B Silicon oxide 25 10 99 <10 35 7B Siliconnitride 25 10 82 <10 36 7C Silicon oxide 25 10 83 <10 37 7D Siliconoxide 25 10 <10 <10 38 7A Silicon oxide 60 10 53 <10 39 7B Silicon oxide60 10 104 <10 40 7B Silicon nitride 60 10 90 <10 41 7C Silicon oxide 6010 90 <10 42 7D Silicon oxide 60 10 34 <10

TABLE 9 Silane-based compound Acid catalyst Solvent Liquid ConcentrationConcentration Concentration composition Type mass % Type mass % Typemass % 9A 6E 1 Sulfuric acid 3 Water 96

TABLE 10 Comparative Liquid Immersing Water contact IPA contact examplecomposition Substrate material Temperature/° C. time/min angle/degreeangle/degree 43 9A Silicon oxide 25 2 110 <10 44 9A Silicon nitride 25 241 <10 45 9A Silicon oxide 60 2 110 <10 46 9A Silicon nitride 60 2 56<10 47 9A Silicon oxide 25 10 109 21 48 9A Silicon nitride 25 10 90 <1049 9A Silicon oxide 60 10 107 13 50 9A Silicon nitride 60 10 92 <10

TABLE 11 Concentration mass % m-Xylene Monomer Monomer Monomer2,2′-Azobis(dimethyl Polymer hexafluoride Formula (13) Formula (14)Formula (15) isobutyrate) 11A 50 9.5 40 0.50 0.17

[Chemical formula 23]

CH₂—CH—COO—(CH₂)₂—(CF₂)₆—F  (13)

[Chemical formula 24]

CH₂—C(CH₃)—COO—(CH₂)₂—(CF₂)₆—F  (14)

[Chemical formula 25]

CH₂═CH—COO—C₂H₄O—CO—C₂H₄—COOH  (15)

TABLE 12 Concentration mass % Liquid composition m-Xylene hexafluoridePolymer 11A 12A 85 15

TABLE 13 IPA Com- contact parative Liquid Substrate Temperature/Immersing angle/ example composition material ° C. time/min degree 5112A Silicon oxide 25 2 <10 52 12A Silicon oxide 60 2 <10 53 12A Siliconoxide 25 10 <10 54 12A Silicon oxide 60 10 <10

1: A liquid composition, comprising: from 0.01-15% by mass of asurfactant (A) having a substituent of Formula (1):C_(n)F_(2n+1)—  (1) wherein n is an integer of from 3-20, and an anionichydrophilic group; and from 0.0001-20% by mass of a compound (B) havinga weight-average molecular weight of from 200-500000 and from 4-30 mmolof an amino group per gram, selected from the group consisting ofpolyethylenimine and a compound having a substituent of Formula (2) or(3):

wherein R¹ and R² are each independently hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group,

wherein R³ and R⁴ are each independently hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group, and X⁻ represents a fluoride ion, achloride ion, a bromide ion, an iodide ion, a fluoroborate ion, aphosphate ion, an acetate ion, a trifluoroacetate ion, a sulfate ion, ahydrogen sulfate ion, a methane sulfate ion, a hydroxide ion, aperchlorate ion or a nitrate ion, and wherein the liquid compound issuitable for imparting alcohol-repellency to a semiconductor substratematerial. 2: The liquid composition according to claim 1, wherein theanionic hydrophilic group has a structure of Formula (4), (5), (6) or(7):

wherein R⁵ and R⁶ each independently represent hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group,

wherein R⁷ and R⁸ each independently represent hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group,

wherein Z represents a metal, hydrogen or a quaternary amine,

wherein Z represents a metal, hydrogen or a quaternary amine. 3: Theliquid composition according to claim 1, wherein the compound (B)comprises a homopolymer or a copolymer comprising, as a startingmaterial monomer, one or more compounds selected from the groupconsisting of: ethyleneimine, prop-2-en-1-amine,N-methylprop-2-en-1-amine, N,N-dimethylprop-2-en-1-amine,N-ethylprop-2-en-1-amine, N-ethyl-N-methylprop-2-en-1-amine,N,N-diethylprop-2-en-1-amine, 2-methylprop-2-en-1-amine,N,2-dimethylprop-2-en-1-amine, N,N,2-trimethylprop-2-en-1-amine,N-ethyl-2-methylprop-2-en-1-amine,N-ethyl-N,2-dimethylprop-2-en-1-amine,N,N-diethyl-2-methylprop-2-en-1-amine, but-2-en-1-amine,N-methylbut-2-en-1-amine, N,N-dimethylbut-2-en-1-amine,N-ethylbut-2-en-1-amine, N-ethyl-N-methylbut-2-en-1-amine,N,N-diethylbut-2-en-1-amine, 2-methylbut-2-en-1-amine,N,2-dimethylbut-2-en-1-amine, N,N,2-trimethylbut-2-en-1-amine,N-ethyl-2-methylbut-2-en-1-amine, N-ethyl-N,2-dimethylbut-2-en-1-amine,N,N-diethyl-2-methylbut-2-en-1-amine, 2,3-dimethylbut-2-en-1-amine,N,2,3-trimethylbut-2-en-1-amine, N,N,2,3-tetramethylbut-2-en-1-amine,N-ethyl-2,3-dimethylbut-2-en-1-amine,N-ethyl-N,2,3-trimethylbut-2-en-1-amine,N,N-diethyl-2,3-dimethylbut-2-en-1-amine, diallylamine,N-allyl-N-methylprop-2-en-1-amine, N-allyl-N-ethylprop-2-en-1-amine,N-allyl-N,N-dimethylprop-2-en-1-amine, a hydrochloride thereof, asulfate thereof, a phosphate thereof, a nitrate thereof and a sulfurdioxide thereof. 4: The liquid composition according to claim 1, whereinthe surfactant (A) comprises one or more selected from the groupconsisting of:N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diaminedioxide,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluoropentylpropyl)propane-1,3-diaminedioxide,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorobutylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluoropentylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluorobutylpropyl)propane-1,3-diaminedioxide,perfluorohexadecanoic acid, perfluoropentadecanoic acid,perfluorotetradecanoic acid, perfluorotridecanoic acid,perfluorododecanoic acid, perfluoroundecanoic acid, perfluorodecanoicacid, perfluorononanoic acid, perfluorooctanoic acid, perfluoroheptanoicacid, perfluorohexanoic acid, perfluoropentanoic acid, perfluorobutanoicacid, perfluorooctanesulfonic acid, perfluoroheptanesulfonic acid,perfluorohexanesulfonic acid, perfluoropentanesulfonic acid,perfluorobutanesulfonic acid, perfluoropropanesulfonic acid,perfluorooctylphosphonic acid, perfluoroheptylphosphonic acid,perfluorohexylphosphonic acid, perfluoropentylphosphonic acid,perfluorobutylphosphonic acid, perfluoropropylphosphonic acid,(1H,1H,2H,2H-perfluorodecyl)phosphonic acid, (1H,1H,2H,2H-perfluorononyl)phosphonic acid,(1H,1H,2H,2H-perfluorooctyl)phosphonic acid,(1H,1H,2H,2H-perfluoroheptyl)phosphonic acid, (1H,1H,2H,2H-perfluorohexyl)phosphonic acid,(1H,1H,2H,2H-perfluoropentyl)phosphonic acid, compounds of Formulae(8)-(11):[CF₃(CF₂)_(m)(CH₂)₂OCH₂CH(OH)CH₂O]₂(O)POH  (8) wherein m is an integerof from 2-7,[CF₃(CF₂)_(k)CH(OH)CH₂O]₂(O)POH  (9) wherein k is an integer of from2-7,[CF₃(CF₂)_(j)(CH₂)₂OCH₂CH(OH)CH₂O](O)P(OH)₂  (10) wherein j is aninteger of from 2-7, and[CF₃(CF₂)_(h)CH(OH)CH₂O](O)P(OH)₂  (11) wherein h is an integer of from2-7, a metal salt thereof and an ammonium salt thereof. 5: The liquidcomposition according to claim 1, wherein the alcohol-repellency isisopropyl alcohol-repellency. 6: The liquid composition according toclaim 1, wherein the semiconductor substrate material comprises one ormore selected from the group consisting of silicon, aluminium, analuminium-copper alloy, tantalum, nickel, tungsten, cobalt, molybdenum,titanium, zirconium, ruthenium, hafnium, platinum, silicon-germanium,germanium, an oxide thereof, a nitride thereof and a carbide thereof. 7:A method for treating a surface of a semiconductor substrate the methodcomprising: bringing the liquid composition of claim 1 into contact withthe semiconductor substrate to impart alcohol-repellency to thesemiconductor substrate. 8: The method according to claim 7, wherein thealcohol-repellency is isopropyl alcohol-repellency. 9: The methodaccording to claim 7, wherein the semiconductor substrate comprises oneor more selected from the group consisting of silicon, aluminium, analuminium-copper alloy, tantalum, nickel, tungsten, cobalt, molybdenum,titanium, zirconium, ruthenium, hafnium, platinum, silicon-germanium,germanium, an oxide thereof, a nitride thereof and a carbide thereof.10: The method according to claim 7, wherein the anionic hydrophilicgroup has a structure of Formula (4), (5), (6) or (7):

wherein R⁵ and R⁶ each independently represent hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group,

wherein R⁷ and R⁸ each independently represent hydrogen or a C1-6 alkyl,alkenyl, alkynyl or aryl group,

wherein Z represents a metal, hydrogen or a quaternary amine, and

wherein Z represents a metal, hydrogen or a quaternary amine. 11: Themethod according to claim 7, wherein the compound (B) comprises ahomopolymer or a copolymer comprising, as a starting material monomer,one or more compounds selected from the group consisting of:ethyleneimine, prop-2-en-1-amine, N-methylprop-2-en-1-amine,N,N-dimethylprop-2-en-1-amine, N-ethylprop-2-en-1-amine,N-ethyl-N-methylprop-2-en-1-amine, N,N-diethylprop-2-en-1-amine,2-methylprop-2-en-1-amine, N,2-dimethylprop-2-en-1-amine,N,N,2-trimethylprop-2-en-1-amine, N-ethyl-2-methylprop-2-en-1-amine,N-ethyl-N,2-dimethylprop-2-en-1-amine,N,N-diethyl-2-methylprop-2-en-1-amine, but-2-en-1-amine,N-methylbut-2-en-1-amine, N,N-dimethylbut-2-en-1-amine,N-ethylbut-2-en-1-amine, N-ethyl-N-methylbut-2-en-1-amine,N,N-diethylbut-2-en-1-amine, 2-methylbut-2-en-1-amine,N,2-dimethylbut-2-en-1-amine, N,N,2-trimethylbut-2-en-1-amine,N-ethyl-2-methylbut-2-en-1-amine, N-ethyl-N,2-dimethylbut-2-en-1-amine,N,N-diethyl-2-methylbut-2-en-1-amine, 2,3-dimethylbut-2-en-1-amine,N,2,3-trimethylbut-2-en-1-amine, N,N,2,3-tetramethylbut-2-en-1-amine,N-ethyl-2,3-dimethylbut-2-en-1-amine,N-ethyl-N,2,3-trimethylbut-2-en-1-amine,N,N-diethyl-2,3-dimethylbut-2-en-1-amine, diallylamine,N-allyl-N-methylprop-2-en-1-amine, N-allyl-N-ethylprop-2-en-1-amine,N-allyl-N,N-dimethylprop-2-en-1-amine, a hydrochloride thereof, asulfate thereof, a phosphate thereof, a nitrate thereof and a sulfurdioxide thereof. 12: The method according to claim 7, wherein thesurfactant (A) comprises one or more selected from the group consistingof:N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diaminedioxide,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluoropentylpropyl)propane-1,3-diaminedioxide,N,N-diethyl-N′,N′-bis(2-hydroxy-3-perfluorobutylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluorohexylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluoropentylpropyl)propane-1,3-diaminedioxide,N,N-dimethyl-N′,N′-bis(2-hydroxy-3-perfluorobutylpropyl)propane-1,3-diaminedioxide,perfluorohexadecanoic acid, perfluoropentadecanoic acid,perfluorotetradecanoic acid, perfluorotridecanoic acid,perfluorododecanoic acid, perfluoroundecanoic acid, perfluorodecanoicacid, perfluorononanoic acid, perfluorooctanoic acid, perfluoroheptanoicacid, perfluorohexanoic acid, perfluoropentanoic acid, perfluorobutanoicacid, perfluorooctanesulfonic acid, perfluoroheptanesulfonic acid,perfluorohexanesulfonic acid, perfluoropentanesulfonic acid,perfluorobutanesulfonic acid, perfluoropropanesulfonic acid,perfluorooctylphosphonic acid, perfluoroheptylphosphonic acid,perfluorohexylphosphonic acid, perfluoropentylphosphonic acid,perfluorobutylphosphonic acid, perfluoropropylphosphonic acid,(1H,1H,2H,2H-perfluorodecyl)phosphonic acid, (1H,1H,2H,2H-perfluorononyl)phosphonic acid, (1H, IH,2H,2H-perfluorooctyl)phosphonic acid,(1H,1H,2H,2H-perfluoroheptyl)phosphonic acid, (1H,1H,2H,2H-perfluorohexyl)phosphonic acid,(1H,1H,2H,2H-perfluoropentyl)phosphonic acid, compounds represented byFormulae (8)-(11):[CF₃(CF₂)_(m)(CH₂)₂OCH₂CH(OH)CH₂O]₂(O)POH  (8) wherein m is an integerof from 2-7,[CF₃(CF₂)_(k)CH(OH)CH₂O]₂(O)POH  (9) wherein k is an integer of from2-7,[CF₃(CF₂)_(j)(CH₂)₂OCH₂CH(OH)CH₂O](O)P(OH)₂  (10) wherein j is aninteger of from 2-7, and[CF₃(CF₂)_(h)CH(OH)CH₂O](O)P(OH)₂  (11), wherein h is an integer of from2-7, a metal salt thereof and an ammonium salt thereof.